Article

pubs.acs.org/crystal

A Systematic Study on the Mesomorphic Behavior of Asymmetrical

1‑Alkyl-3-dodecylimidazolium Bromides
Mei Yang,† Bert Mallick,† and Anja-Verena Mudring*,†,‡
†
Anorganische Chemie III − Materials Engineering and Characterization, Fakultät für Chemie and Biochemie, Ruhr-Universität
Bochum, 44780 Bochum, Germany
‡
Department of Materials Science and Engineering, Iowa State University and Ames Laboratory, Ames, Iowa 50011, United States
*
S Supporting Information

ABSTRACT: To determine the essential parameters for mesophase formation

in imidazolium-based ionic liquids (ILs), a library of 1-alkyl-3-dodecylimida-
zolium bromides was synthesized, abbreviated as CnC12, where 0 ≤ n ≤ 13, as
the general notion is that a dodecyl side chain would guarantee the formation
of an ionic liquid crystal (ILC). All salts were fully characterized by NMR
spectroscopy and mass spectrometry. Their thermal properties were recorded,
and mesophase formation was assessed. An odd−even effect is observed for 5 ≤
n ≤ 10 in the temperatures of melting transitions. While the majority of this
series, as expected, formed mesophases, surprisingly compounds C2C12 and
C6C12 could not be classified as ILCs, the latter being a room temperature IL,
while C2C12 is a crystalline solid with melting point at 37 °C. The single
crystal structure of compound 1-ethyl-3-dodecylimidazolium bromide (C2C12)
was successfully obtained. Remarkably, the arrangement of imidazolium cores
in the structure is very complicated due to multiple nonclassical hydrogen
bonds between bromide anions and imidazolium head groups. In this arrangement, neighboring imidazolium rings are forced by
hydrogen bonds to form a “face-to-face” conformation. This seems to be responsible for the elimination of a mesophase. To
conclude, the general view of a dodecyl chain being a functional group to generate a mesophase is not entirely valid.

1. INTRODUCTION functional materials and have attracted significantly increasing

Ionic liquid crystals (ILCs) are a class of ionic liquid (IL)
materials possessing the ability to form a liquid crystalline state.
The liquid crystalline state is an intermediate state between
perfect ordered crystalline solid state and that of the total
disordered liquid state. The molecules in this state are ordered
along at least one spatial coordinate.1 ILCs are ionic
compounds and are also amphiphiles in general. Their
physiochemical properties such as melting points, viscosity,
conductivity, and lipophilicity can be tuned by varying cation
and anion combinations like in ILs.2 The combination of the
partially ordered properties and IL features of these amphiphilic
compounds has rendered them one of the most attractive
materials. The physicochemical properties of ILCs have been
extensively studied based on their structural changes.3−7 The
importance of ILCs has been realized in diverse applications,
such as ion-conductive materials,8 organized reaction media, or
self-assembled nanostructured materials.1,9,10 Thanks to the
formation of ordered domains, in which reactions could occur,
if used as reaction media ILCs may supply an additional
reaction control.11−14 In addition, ILCs may also exhibit
catalytic activities and/or play an important role in selectivity.15
For example, ILCs and long chain alkyl ILs have been used in
an “ILC-SILP” (SILP: supported ionic liquid phases) concept
for a “medium induced selectivity” during Ni-NHC-catalyzed
olefin dimerization.16,17 Although they are also highly attractive
interest in recent years, ILCs have not received the same in-
depth attention.
Nowadays, imidazolium-based cations are by far the most
popular examples for both ILs and ILCs.18−21 The correlation
between the properties and structural changes of imidazolium-
based ILs has been systematically investigated, regarding a wide
variety of changing cationic and anionic structures.3,4,6 The
fundamental understanding of the effect of alkyl groups on
physiochemical properties, including thermal behavior, viscos-
ity, density, and microscopic ion dynamics has been reported.
According to the findings of us and others,22 a dodecyl unit
could be considered as a functional group responsible for liquid
crystalline behavior; that is, for 1-alkyl-3-methylimidazolium,
mesomorphism can be observed when the alkyl chain contains
12 or more carbon atoms.6 However, with regard to these long
chain-bearing ILs, only 1-alkyl-3-methylimidazolium and sym-
metrical 1,3-dialkylimidazoliums (where alkyl ≥ dodecyl) have
been investigated for their ILC behavior. Only little is
understood with respect to the fundamental aspects of LC
formation from asymmetric long chain 1,3-dialkylimidazolium
compounds. Correlation of varying alkyl chain length with the
Received: September 19, 2013
Revised: February 11, 2014
Published: February 12, 2014

© 2014 American Chemical Society 1561 dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design
changes in physicochemical properties of ILs bearing one
dodecyl unit still needs to be explored to facilitate the
molecular design of ILCs. Furthermore, previous investigations
of imidazolium-based ILs and ILCs have mostly focused on
even numbered chain lengths; ILs or ILCs with odd number
alkyl chains are very seldom reported.
For this reason, a series of 1-alkyl-3-dodecylimidazolium
bromides ([CnC12IM]Br, n = 0 − 13) was investigated. The
influence of these systematic structural variations on the
physicochemical properties was studied, focusing on their
thermal behavior and liquid crystalline properties. The thermal
and structural properties were investigated via differential
scanning calorimetry (DSC), polarizing optical microscopy
(POM), and temperature dependent X-ray diffraction (SAXS).
For convenience, we use the same designations for the
compounds as is used in our previous report.22 The compounds
are named by the number of carbon atoms in the two alkyl
chains at the first and third positions of the imidazolium ring.
For example, [C5IMC12]Br, 1-pentyl-3-dodecylimidazolium
bromide, as C5C12 and [C6IMC12]Br, 1-hexyl-3-dodecylimi-
dazolium bromide, as C6C12.
2. EXPERIMENTAL SECTION
2.1. Sample Preparation. The synthesis and sample handling of
anhydrous salts were carried out using standard Schlenk and argon-
glovebox techniques. All the bromide compounds were hygroscopic.
The samples were dried under 10−6 mbar at 60 °C for 3 days. All the
sample preparations for further analytics were carried out in an argon-
glovebox.
2.2. Synthesis. Acetonitrile (99.5%), ethyl acetate (95%),
methanol (99%), dichloromethane (99.9%), and tetrahydrofuran
(extra dry, >99%) were used as received from J.T. Backer (Deventer,
Holland). Hydrobromic acid (47%) was obtained from Merck
(Darmstadt, Germany). 1-Propylimidazole (98%), 1-hexylimidazole
Scheme 1. 1-Alkyl-3-dodecylimidazolium Cations under
Investigationa
a
Bromide was used as the counter ion.
1562
Article
(98%), and 1-octylimidazole (98%) were purchased from IoLiTec
(Heilbronn, Germany). 1-Ethylimidazole (95%), 1-butylimidazole
(98%), imidazole (99.5%), sodium hydride (95%), and all 1-
bromoalkanes were purchased from Sigma-Aldrich (Steinheim,
Germany). All chemicals were used as received without further
purification.
1-Dodecylimidazole was synthesized using a reported procedure.20
After the purification procedure, the product was obtained as a yellow-
brownish oil. Experimental details are provided in Supporting
Information. Yield = 71%. 1H NMR (298 K, 200 MHz, DMSO-d6):
δ [ppm] = 0.86 (3H, t), 1.04−1.46 (14H, m), 1.64−1.83 (2H, m),
3.71−4.09 (2H, m), 6.92 (2H, dd), 7.43 (1H, s).
[C0C12]Br was prepared by dropwise addition of a slight excess of
concentrated hydrobromic acid (4 mL) to 1-dodecylimidazole at 0 °C
(1.0 g, 4.2 mmol) in diethyl ether. The bromide salt precipitated as a
white solid after cooling at −30 °C overnight. Unlike [C0C13]Br,22
[C0C12]Br was highly hygroscopic. The product was filtered under
inert environment, washed repeatedly with ethyl acetatem and dried in
a vacuum for at least 3 days at 60 °C. Yield = 48%. 1 H NMR (200
MHz, DMSO-d6): δ [ppm] = 0.83 (3H, t), 1.22 (22H, m), 1.78 (2H,
t), 4.16 (2H, t), 7.68 (1H, s), 7.78 (1H, s), 9.15 (1H, s). ESI-MS
(positive, ([%])) m/z = 265.1 [M − Br]+ (100).
C5C12, C7C12, C9C12, C10C12, C11C12, C12C12, and C13C12
were synthesized with the general method for 1,3-dialkylimidazolium
bromides via direct alkylation of the respective 1-dodecylimidazole
with alkyl bromide in a 1:1.1 molar ratio in acetonitrile.23
Syntheses of C1C12, C2C12, C3C12, C4C12, C6C12, and C8C12
followed the same procedure except 1-methylimidazole, 1-ethyl-
imidazole, 1-propylimidazole, 1-butylimidazole, 1-hexylimidazole, and
1-octylimidazole were alkylated using 1-bromododecane.
Compounds C0C12, C1C12, and C2C12 were obtained as
crystalline solids; compounds C3C12, C4C12, and C5C12 are viscous
room temperature ionic liquids (RTILs); C6C12 is obtained as a
crystalline solid, while C7C12, C8C12, C9C12, and C10C12 are
viscous liquids or wax-like solids. The analytical data are reported
below.
[C1C12]Br was synthesized from 1-methylimidazole (2.5 g, 30.0
mmol) and 1-bromododecane (8.3 g, 33.0 mmol). Yield = 91%. 1H
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.82 (3H, t), 1.20
(17H, m), 1.74(2H, t), 3.81 (s, 3H), 4.17 (2H, t), 7.61 (2H, s), 9.27
(1H, s). ESI-MS (positive, ([%])) m/z = 251.1 [M − Br]+ (100).
[C2C12]Br was synthesized from 1-ethylimidazole (3 g, 29.6 mmol)
and 1-bromododecane (7.4 g, 30.0 mmol). Yield = 90%. 1H NMR
(298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (3H, m), 1.23 (18H,
m), 1.41(3H, t), 1.77 (m, 2H), 4.17 (4H, qn), 7.78 (2H, m), 9.21 (1H,
s). ESI-MS (positive, ([%])) m/z = 268.3 [M − Br]+ (100).
[C3C12]Br was synthesized from 1-propylimidazole (2.5 g, 23.4
mmol) and 1-bromododecane (6.3 g, 25.7 mmol). Yield = 72%. 1H
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.83 (6H, m), 1.22
(18H, m), 1.78 (4H, m), 4.13 (4H, m), 7.81 (2H, s), 9.27 (1H, s).
ESI-MS (positive, ([%])) m/z = 282.3 [M − Br]+ (100).
[C4C12]Br was synthesized from 1-butylimidazole (3 g, 24.2 mmol)
and 1-bromododecane (6.6 g, 26.6 mmol). Yield = 84%. 1H NMR
(298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.86 (6H, m), 1.22 (22H,
m), 1.77 (4H, m), 4.17 (4H, m), 7.80 (2H, m), 9.27 (1H, s). ESI-MS
(positive, ([%])) m/z = 296.1 [M − Br]+ (100).
[C5C12]Br was synthesized from 1-dodecylimidazole (3 g, 12.7
mmol) and 1-bromopentane (2.1 g, 13.9 mmol). Yield = 84%. 1H
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22
(24H, m), 1.79 (4H, m), 4.16 (4H, m), 7.82 (2H, m), 9.29 (1H, s).
ESI-MS (positive, ([%])) m/z = 310.3 [M − Br]+ (100).
[C6C12]Br synthesized from 1-hexylimidazole (3 g, 19.3 mmol)
and 1-bromododecane (5.0 g, 20.0 mmol). Yield = 84%. 1H NMR
(298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22 (26H,
m), 1.78 (4H, m), 4.16 (4H, m), 7.81 (2H, s), 9.29 (1H, s). ESI-MS
(positive, ([%])) m/z = 324.4 [M − Br]+ (100).
[C7C12]Br was synthesized from 1-dodecylimidazole (3 g, 12.7
mmol) and 1-bromoheptane (2.5 g, 13.9 mmol). Yield = 84%. 1H
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22
dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design Article

(28H, m), 1.78 (4H, m), 4.16 (4H, m), 7.80 (2H, s), 9.25 (1H, s). peaks at positive heat flow. DSC runs included heating and subsequent
ESI-MS (positive, ([%])) m/z = 338.3 [M − Br]+ (100). cooling at 5 °C/min. Given temperatures correspond to the onset of
[C8C12]Br synthesized from 1-octylimidazole (3 g, 16.3 mmol) and the respective thermal process.
1-bromododecane (4.1 g, 16.5 mmol). Yield = 67%. 1H NMR (298K, 2.8. Polarizing Optical Microscopy. The POM pictures of
200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22 (30H, m), 1.78 mesophases were acquired with an Axio Imager A1 microscope (Carl
(4H, m), 4.16 (4H, m), 7.80 (2H, s), 9.30 (1H, s). ESI-MS (positive, Zeiss MicroImaging GmbH, Göttingen, Germany) equipped with a
([%])) m/z = 352.4 [M − Br]+ (100). hot stage, THMS600 (Linkam Scientific Instruments Ltd., Surrey,
[C9C12]Br was synthesized from 1-dodecylimidazole (3 g, 12.7 UK), and a Linkam TMS 94 (Linkam Scientific Instruments Ltd.,
mmol) and 1-bromononane (2.9 g, 13.9 mmol). Yield = 91%. 1H Surrey, UK) temperature controller and crossed polarizers. Images
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22 were recorded at a magnification of 100× as video with a digital
(32H, m), 1.78 (4H, m), 4.15 (4H, m), 7.80 (2H, s), 9.23 (1H, s). camera after initial heating during the cooling stage. Heating and
ESI-MS (positive, ([%])) m/z = 366.2 [M − Br]+ (100). cooling rates were 5 K/min−1. For the measurement, the samples were
[C10C12]Br was synthesized from 1-dodecylimidazole (3 g, 12.7 placed under argon between two coverslips which were sealed with
mmol) and 1-bromodecane (3.1 g, 13.9 mmol). Yield = 90%. 1H NMR two-component adhesive (UHU plus 300, UHU GmbH & Co. KG,
(298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22 (34H, Bühl, Germany).
m), 1.78 (4H, m), 4.12 (4H, m), 7.81 (2H, s), 9.27 (1H, s). ESI-MS
(positive, ([%])) m/z = 380.3 [M − Br]+ (100). 3. RESULTS AND DISCUSSION
[C11C12]Br was synthesized from 1-dodecylimidazole (3 g, 12.7 3.1. Structural Analysis. Single crystals of compound
mmol) and 1-bromoundecane (3.3 g, 13.9 mmol). Yield = 90%. 1H
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.84 (6H, m), 1.22
C2C12 could be obtained from cooling the molten compound
(36H, m), 1.77 (4H, m), 4.15 (4H, m), 7.80 (2H, s), 9.23 (1H, s). to room temperature in the form of flat, colorless needles.
ESI-MS (positive, ([%])) m/z = 394.3 [M − Br]+ (100). Experiments to obtain single crystals of the other compounds in
[C12C12]Br was synthesized from 1-dodecylimidazole (3 g, 12.7 this series of sufficient quality for X-ray structure analysis failed
mmol) and 1-bromododecane (3.5 g, 13.9 mmol). Yield = 85%. 1H so far. Compound C2C12 crystallizes unexpectedly in the
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.82 (6H, m), 1.22 triclinic space group P(1̅) (No. 2), not isotypic with C2C11,22
(38H, m), 1.77 (4H, m), 4.16 (4H, m), 7.81 (2H, s), 9.25 (1H, s). which crystallizes in the monoclinic space group P21/c (No.
ESI-MS (positive, ([%])) m/z = 408.1 [M − Br]+ (100). 14). Crystallographic data, data collection, and structure
[C13C12]Br was synthesized from 1-dodecylimidazole (2 g, 9.5 refinement details are given in Table 1. The asymmetric unit
mmol) and 1-bromotridecane (2.8 g, 10.5 mmol). Yield = 88%. 1H
NMR (298 K, 200 MHz, DMSO-d6) δ [ppm] = 0.85 (6H, m), 1.22
(42H, m), 1.78 (2H, m), 4.18 (4H, m), 7.80 (2H, s), 9.22 (1H, s). Table 1. Crystallographic and Refinement Details for C2C12
ESI-MS (positive, ([%])) m/z = 422.4 [M − Br]+ (100). empirical formula C17H33BrN2
2.3. 1H NMR Spectra. were recorded on a Bruker DPX 250b
formula weight 345.35 g/mol
(operating at 200.1 MHz for 1H) (Bruker, Germany).
crystal system triclinic
2.4. ESI Mass Spectra. were recorded on an Esquire 6000
instrument (Bruker, Karlsruhe, Germany) applying the following space group P1̅
parameters: sputtering voltage 4 kV; nebulizer pressure 10−20 psi; unit cell a = 11.0090 Å; b = 12.1650 Å; c = 23.1770 Å;
dimensions α = 94.727°; β = 95.591°; γ = 110.903°
drying gas 5−10 L/min, 300 °C; flow rate 240 μL/h. For all mass
spectrometric measurements, the ILs samples were prepared as 1 mg/ volume 2862.9 Å
mL solutions in acetonitrile. Z 6
2.5. Crystal Structure Analysis. Crystals of [C2C12]Br were temperature 170 K
obtained by cooling the molten compound to room temperature. calculated density 1.20 mg/cm3
Suitable single crystals were sealed in Lindeman glass capillaries. All absorption 2.149 mm−1
data were collected on a Stoe IPDS-I single-crystal X-ray coefficient
diffractometer with graphite monochromated Mo Kα radiation (λ = Θ-range for data 2.3 to 25.0°
0.71073 Å at 170 K). Crystal structure solution by direct methods collection
using SIR 92 yielded the heavy atom positions. Refinement with reflections 9477/6258
SHELXL-97 allowed for the localization of the remaining atom collected/
unique
positions. Hydrogen atoms were added and treated in the riding atom
mode. Data reduction was carried out with the program package X- refinement full-matrix least-squares on F2
method
Red, and numerical absorption correction was carried out with the
data/parameters 6258/547
program X-Shape. To illustrate the crystal structures, the program
Diamond 3 was used. goodness-of-fit on 0.785
F2
2.6. Temperature-Dependent SAXS Experiments. Small-angle
final R indices R1 = 0.029; wR2 = 0.056
X-ray scattering (SAXS) measurements were carried out at the A2 [I > 2σ(I)]
Beamline of DORIS III, Hasylab, DESY, Hamburg, Germany, at a fixed R indices (all R1 = 0.055; wR2 = 0.060
wavelength of 1.5 Å. The data were collected with a MarCCD data)
detector. The detector was calibrated with silver behenate. The
sample−detector position was fixed at 635.5 mm. For measurements,
the samples were placed in a copper sample holder between aluminum contains three crystallographically independent [C2C12]+
foil. The sample temperature was controlled by a JUMO IMAGO 500 cations and three Br− as counterions (Figure 1). In contrast
multichannel process and program controller. Data reduction and to compound C2C11, in which all undecyl chains form a linear
analysis, correction or background scattering and transmission were structure of favored all-trans configurations, in C2C12 distinct
carried out by using the program a2tool (Hasylab).
differences conformations of each of the three crystallo-
2.7. Differential Scanning Calorimetry (DSC). The DSC
measurements were performed with a computer-controlled Phoenix graphically independent cations in the asymmetric unit are
DSC 204 F1 thermal analyzer (Netzsch, Selb, D) with argon as apparent.
protection gas. The samples were placed in aluminum pans which were One of the cations can be characterized by a rodlike shape
cold-sealed under argon. Experimental data are displayed in such a way with one dodecyl chain and one ethyl chain being almost
that exothermic peaks occur at negative heat flow and endothermic perpendicular to the imidazolium core plane. Both starting C
1563 dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design Article

Figure 1. Asymmetric unit of C2C12; hydrogens are omitted for

clarity.

atoms in the two alkyl chains are located in the same plane as
the imidazolium core. The dodecyl chain and imidazolium core
plane form an angle (defined as the angle between the Figure 2. Packing diagram of C2C12. View along the crystallographic
imidazolium ring centroid and the terminal C atom of alkyl b axis (top) and a axis (bottom).
chain) of 95°. The terminal C atom of ethyl chain is tilted with
respect to the imidazolium ring at an angle of 111°. The
dodecyl chain shows all-trans conformation, aside the bond
between the first and the second C atoms, which exhibits a
trans−gauche conformation with a torsion angle of 62°. The
imidazolium core plane is almost parallel to the ab plane,
forming an angle of 6°.
In the second [C2C12]+ cation, the angle between the
dodecyl chain and imidazolium core plane increases to 143°.
The terminal C atom of ethyl chain forms an angle of 110° with
respect to the imidazolium. The dodecyl chain adopts an all-
trans conformation. The imidazolium core plane tilts with
respect to the ab plane at an angle of 59°.
The third [C2C12]+ cation adopts a similar conformation to
the second one, aside from a gauche conformation around the
bond between the second and the third C atoms in the dodecyl
chain, with a torsion angle of 74°. The angle between the
imidazolium core plane and the ab plane is 76°.
The all-trans sections of the dodecyl chains belonging to the
first and second cations lie in planes roughly parallel to one
another and to the crystallographic a-axis, while that of the
third cation lies roughly parallel to the crystallographic b-axis.
Compound C2C12 forms a layered structure, in which
hydrophilic and hydrophobic regions can be observed. The
hydrophobic regions are formed by interdigitated dodecyl
chains of imidazolium cations with a repeating layer distance of
25.4 Å. Three cations form a unit, and units layer with different
orientations (Figure 2). The interdigitation is observed in both
the crystallographic ac and bc planes. The hydrophilic regions
are formed by the charged imidazolium cations with the ethyl
chains and bromide anions. Nonclassical hydrogen bonds
between cations and anions can be discussed. Five neighboring
imidazolium rings can be connected to a bromide anion via Figure 3. Hydrogen bonding interactions in detail for C2C12 (top);
hydrogen bonds. Not only the protic C-positions on the conformations of the cation units, due to hydrogen bonding (middle
imidazolium cores but also protons from both starting C atoms and bottom).
on ethyl and dodecyl chains participate the hydrogen bonding
(Figure 3, top). The hydrogen bonds force the trication units to
take the following conformation: the imidazolium ring in the tilting angle of 70° (Figure 3, middle); the two imidazolium
first cation facing the imidazolium core in the third one, with a rings of the second cations stay parallel to each other and take a
1564 dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design Article

face-to-face conformation (Figure 3, bottom). The hydrogen

bonding interactions are summarized for clarity in Table 2.

Table 2. Hydrogen Bonds in C2C12

D−A/Å D−H/Å H···A/Å D−H···A/°
C17−H17···Br 3.709 0.970 3.085 123.379
C12−H12···Br 3.502 0.930 2.778 135.414
C28−H28B···Br 3.896 0.970 2.984 157.144
C38−H38B···Br 3.739 0.970 2.967 137.352
C25′−H25′···Br 3.711 0.930 2.832 158.231
C35′−H35′···Br 3.785 0.930 2.866 169.933

3.2. Thermal Investigations. The thermal properties of all

compounds were investigated by polarizing optical microscopy
(POM) and differential scanning calorimetry (DSC). Thermal
transitions are summarized in Table S1 (see Supporting
Information). The existence of mesophases was examined
with POM and SAXS measurements.
For clarity, we will discuss these compounds in five separate
groups according to their characteristic thermal behavior.
The first group contains compounds C0C12, C1C12, and
C2C12. Their DSC scans at 5 K/min are shown in Figure 4.
All these three compounds show suppression of crystal-
lization. In the first heating scan, the crystalline solids, as
obtained from the synthesis, show a clear endothermic
transition around 40 °C, which can be identified as a melting
point. In contrast to C2C12, compounds C0C12 and C1C12
exhibit a liquid crystalline state. For these two compounds,
small endothermic transitions are apparent at 87 °C for C0C12
and 100 °C for C1C12, which can be determined to be liquid
crystalline ↔ isotropic liquid (LC ↔ L) transitions. The LC ↔
L transitions for both C0C12 and C1C12 reverse in the cooling
scans with almost the same enthalpies. An extensive super-
cooling of the crystallization process was observed for all three
compounds. However, the enthalpy value of LC ↔ S
transitions, or L ↔ S transition in the case of C2C12, is
significantly smaller than the value from the heating scans. In
the second heating runs, a cold crystallization process preceding
the melting transitions is observed for C0C12 and C2C12, and
for C1C12 two of these are observed. These effects could be
determined as solid−solid transitions (S ↔ S) by POM and
SAXS, due to an order−disorder transition of the long alkyl
chains. All further heating cycles were reproducible and similar
to the first cooling and second heating scans.
The second group is comprised of compounds C3C12,
C4C12, and C5C12, which are liquids at room temperature and
show liquid crystalline behavior during the second heating run
at lower temperature. All the following heating and cooling
DSC traces are identical to the traces from the first cycle. To
elucidate the thermal behavior of these compounds, POM
investigations were performed. The traces from second heating
and cooling scans with the corresponding POM images are Figure 4. DSC scans for C0C12, C1C12, and C2C12 at 5 K/min.
shown in Figure 5. POM analyses of these samples consistently
show the characteristic focal conical textures of a SmA phase. In observed before they melt into isotropic liquids. No visible
the first cooling scans, C3C12, C4C12, and C5C12 crystallized change could be observed for this thermal effect by POM and
at −39 °C, −37 °C, and −19 °C, respectively. During the SAXS measurements (vide infra). It could be associated to the
second heating, they show a liquid crystalline behavior after an formation of another mesophase with similar order. Since no
endothermic peak (see POM image in Figure 5). Compound texture changes have been observed in POM, we believe this
C4C12 exhibits even a cool crystallization prior to this S ↔ LC unidentified mesophase could be considered as a smectic phase,
transition, which could be observed from the POM measure- too. For compound C5C12, a broad endothermic effect
ment. While the compounds C3C12 and C4C12 are situated in corresponding to a melting process appears at 7.5 °C with a
liquid crystalline state, another exothermic transition is shoulder peak at 18 °C, which can be considered as two back-
1565 dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design
Figure 5. DSC thermograms of C3C12, C4C12, and C5C12 with
corresponding POM images.
to-back thermal effects. These two transitions are observed
separately in the cooling scans, as a result of supercooling. This
transition can be considered as the transition between the
unidentified mesophases, SmX ↔ SmA.
Surprisingly, compound C6C12 does not show any liquid
crystalline properties. The thermal behavior corresponds to a
typical IL. Crystals of C6C12 were obtained by recrystallization
from solution. During the first heating DSC scan, a clear
melting point is shown at 35 °C. Once molten, the DSC shows
only a glass transition in the thermal cycle. Obviously, the
recrystallization from the melt is hindered. The thermal
behavior of C6C12 illustrated in Figure 6.
The fourth group contains compounds C7C12, C8C12,
C9C12, and C10C12. Generally, the DSC traces are simple and
show two transitions, the melting point (S ↔ LC transition)
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Figure 6. DSC scans for C6C12 at 5 K/min. Inset shows an enlarged
view of DSC scans in the region of the glass transitions.
and the clearing point (LC ↔ L-transition). C7C12 and
C8C12 show only a broad endothermic peak in the first heating
scans, which is a result of two overlapping thermal effects.
These two effects are observed separately in the cooling scans,
due to supercooling. For C8C12, these two effects are visible as
two successive narrow peaks in the second heating scan.
Further heating and cooling cycles of C8C12 show thermal
behavior identical to the first cooling and second heating scans.
For C7C12, C9C12, and C10C12, all the subsequent thermal
cycles are identical to the first heating cycle. The traces from
the second heating cycle are shown in Figure 7.
C11C12, C12C12, and C13C12 make up the final group. All
of these compounds show only melting points (S ↔ LC
transition) and clearing points (LC ↔ L-transition) in the first
heating scans. In the cooling scan, they display crystal
polymorphism. At lower temperature, multiple transitions are
visible in the DSC traces, which can be attributed to crystal−
crystal transitions. These thermal effects are reversed in the
second heating run. For C12C12 and C13C12, exothermic S ↔
S transitions preceding the melting points are observed (Figure
8).
The temperature range (obtained from the collected thermal
data of the melting points (S ↔ LC or S ↔ L-transition) and
clearing points (LC ↔ L-transition)) of mesophase for all the
compounds is shown in Figure 9. Two significant trends for
both melting point and clearing point are observed on either
side of n = 6: for 1 ≤ n ≤ 5 the transition temperatures decrease
with increasing chain length; after n < 6, the inverse trend is
observed. This effect is in agreement with the observations of
Rocha et al. for 1-alkyl-3-methylimidazolium bis-
(trifluoromethanesulfonyl)imide salts.24 Inverse trends both in
enthalpies and entropies with the increase of the cation alkyl
chain length either side of 1-hexyl-3-methylimidazolium cation
have been reported. The trend changes around n = 6 can be
related to structural modifications and indicate the beginning of
a new regular type of molecular interaction. The falling trends
up to n = 6 can be explained by considering the decreasing van
der Waals forces between the long alkyl chains, as shorter alkyl
chains are brought into and disrupt the highly ordered dodecyl
chain stacks. The discontinuity observed at n = 6 could be due
to compensation of destructive interactions from disorder of
shorter alkyl chains by cohesive forces from ordered dodecyl
dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design Article

Figure 7. DSC scans for C7C12, C8C12, C9C12, and C10C12 at 5 K/min.

Figure 8. DSC scans for C11C12, C12C12, and C13C12 at 5 K/min.

chains. For n > 6, the cohesive intermolecular interactions group. Remarkably, C6C12 exhibits a similar melting point to
through van der Waals forces rise with each additional −CH2− those of C0C12, C1C12, and C2C12. This indicates the hexyl
1567 dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design
Figure 9. The phase transition diagram of [CnC12]Br from DSC at 5
°C/min. For compound C6C12, the value from first DSC heating scan
was taken. For the rest of the compounds, all the transitions are
reversible, and the thermal data from the second heating scans were
taken. For clarity, the solid−solid and LC−LC transitions are not
shown.
groups could be packed into a crystal lattice almost as well as
methyl or ethyl groups, offering an explanation for the
discontinuity at this value. The same effect of hexyl groups
has been observed by Dzyuba et al. for symmetrical 1,3-
dialkylimidazolium hexafluorophosphate.25 A well-packed
crystal lattice probably exhibiting low flexibility, could explain
why C6C12 is not favored for mesophase formation. In
addition, we observed a distinct odd−even effect for 5 ≤ n ≤ 10
in the melting transitions, which is reflected in the state of the
compounds at room temperature. The melting points of the
compounds with even n are higher than their immediate
neighbors with odd lengths of n. C5C12, C7C12, and C9C12
exist as viscous but fluid liquids, while C6C12, C8C12, and
C10C12 are wax-like solids (Figure 10). This phenomenon is
Figure 10. Demonstration of even−odd-effect: compounds C5C12,
C6C12, C7C12, C8C12, C9C12, and C10C12 at room temperature.
contrary to the even−odd effect discussed by Holbrey and
Seddon for 1-alkyl-3-methylimidazolium with long chains.6 Our
observation could be a reflection of the ion dynamics in ILs,
which has also been observed for viscosity with a similar even−
odd effect.26 A high local order in systems with even chain
lengths observed by MD simulations was reported by Wang
and Voth; they showed the diffusion constants of compounds
with odd alkyl chain lengths are smaller than the diffusion
constants of compounds with even chain lengths.27 In contrast,
the clearing points increase rapidly with rising n, for n ≥ 7, and
no even−odd effect is observed.
3.3. Mesophase Investigations with POM and SAXS.
Liquid crystalline mesophases were observed during the process
of heating and cooling for all compounds except C2C12 and
C6C12. The temperature ranges and the existence of the
aforementioned mesophases for the 12 compounds were
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confirmed by polarizing optical micrographs and X-ray
scattering in the small angle range. The corresponding POM
images for all the mesogens are shown in Figure 11.
Compounds C0C12, C5C12, C8C12, and C12C12 show an
oily streak texture, and the other compounds show a focal conic
fan texture. Both textures indicate a smectic mesophase. The
layer spacing distances d of all the compounds in the crystalline
states and the ionic liquid crystalline phases are summarized in
Table 3.
The SAXS data supply an insight into the alignment in
crystalline and liquid crystalline states. For clarity, the layer
spacing distances d of all the compounds in the crystalline
states and the ionic liquid crystalline phases are plotted with n,
the length of the varying alkyl chain is shown in Figure 12. As is
well-known, imidazolium-based ILs with long alkyl chains form
layered structures by interdigitating the long alkyl tails. During
heating and cooling processes, the rod-shaped molecules move
along the alkyl axis, so that the attractive van der Waals forces
maintain a mesophase formation.28 The layer spacing increases
on transforming from the crystal to the mesophase for
compound C0C12, C1C12, C12C12, and C13C12, which
indicates that the structure undergoes a formation of smectic A
phase by decreasing the angle of tilt with respect to the layer
normal and/or decreasing of the interdigitated region. For
compounds C7C12, C8C12, C9C12, C10C12, and C11C12,
the layer spacing in the mesophase is smaller than the layer
spacing in the crystal. This indicates that in the mesophase, the
alkyl chains of cations are tilted with respect to the layer
normal. In this way, a smectic C phase is formed. Smaller d
values in the crystalline state indicate a high extent of alkyl
chain interdigitation, which creates greater cohesive intermo-
lecular interactions. These strong interactions lead to a higher
melting point. The d values in crystalline phases for compounds
C3C12, C4C12, and C5C12 could not be measured, since their
crystallizations occur at very low temperatures, which were not
accessible under the given experimental conditions. The
structural relationship between the crystalline and liquid
crystalline states can be discussed for n ≤ 2 and 6 ≤ n ≤ 13.
The layer spacing increases by ca. 4 Å from C0C12 to C1C12.
It could be argued as a consequence of the reorganization due
to the addition of a methyl group. The layer distance increases
from n = 1 to n = 2 by around 1.5 Å, corresponding roughly to
the length of a −CH2− group. The lowest d value is observed
for n = 6. This confirms the previous declaration: Hexyl groups
pack well into the crystal lattice. Full interdigitation is necessary
to counteract the destructive interactions. From n = 7 to n = 9,
the value of d rises again by 1.5 Å with the addition of each
methylene unit. The lower value at n = 10 compared to its
immediate neighbors with odd alkyl chain lengths is indicative
of significant interdigitation of alkyl chains and thus fortified
van der Waals forces. This is in agreement with our observation
of a higher melting point. The dramatic fall of around 8.5 Å
from n = 11 to n = 12 and the sharp rise of 5 Å from n = 12 to n
= 13 could possibly be associated with a twist of the alkyl
chains, meaning that the molecules adopt a V-shape instead of
linear rod shape. Formation of a V-shape for compound
[C12C12]I has been reported by Wang et. al.29 Since the layer
spacing of C0C12 and C12C12 is quite similar, we believe their
alkyl chains must be tilted with respect to the layer normal at
the same angle. The conformations of these two compounds
are illustrated in Figure 13.
dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design Article

Figure 11. Polarizing optical microscopy images: (a) C0C12 at 56 °C; (b) C1C12 at 67 °C; (c) C3C12 at −8 °C; (d) C4C12 at −10 °C; (e)
C5C12 at −20 °C; (f) C7C12 at 0 °C; (g) C8C12 at 25 °C; (h) C9C12 at 40 °C; (i) C10C12 at 60 °C; (j) C11C12 at 70 °C; (k) C12C12 at 60 °C;
(l) C13C12 at 40 °C.

Table 3. Layer Distances d/Å in the Crystalline States and the Liquid Crystalline Phases
C0C1 C1C12 C2C12 C3C12 C4C12 C5C12 C6C12
dCr [Å] 20.6 24.4 26.2 b b b 16.5
dLC [Å] 29.9 29.5 a 29.6 24.8 25.0 a
C7C12 C8C12 C9C12 C10C12 C11C12 C12C12 C13C12
dCr [Å] 25.4 26.8 28.3 25.8 27.4 19.1 24.2
dLC [Å] 23.3 23.4 23.3 23.9 25.5 28.0 33.4

4. CONCLUSIONS second heating run at lower temperature (≤−20 °C); (iii)

We have attempted to determine the essential parameters for
mesophase formation of imidazolium-based ILs by varying the
cation geometry. According to the results from previous
report,22 N-dodecyl chains appear to be essential for
mesomorphic behavior. Therefore, a library of 14 1-alkyl-3-
dodecylimidazolium based bromides salts was synthesized. The
thermal transitions and liquid crystalline behavior have been
studied by DSC, POM, and SAXS. The structure of compound
C2C12 could be obtained from the single crystal X-ray analysis.
Compound C2C12 crystallizes in the triclinic space group
P(1̅) (No. 2). The asymmetric unit contains three cations with
distinct conformations in contrast to compound C2C11,22 in
which all undecyl chains form a linear moiety of favored all-
trans configurations.
All the compounds can be considered as ILs, as their melting
points are below 100 °C. Thermotropic liquid crystalline
behavior can be observed for all the compounds except C2C12
and C6C12. On the basis of their distinct thermal behavior,
these salts can be described in four groups: (i) materials with
surpressed crystallization; (ii) compounds that are liquid at
room temperature and exhibit cold crystallization during the
1569
C6C12, an IL exhibiting a melting point in the first heating scan
and only glass transitions in following heating cycles; (iv)
compounds displaying crystalline polymorphism at lower
temperature.
The variation of the melting points with chain length n,
where n is the length of the varying alkyl chain, shows clearly
two trends: For 1 ≤ n ≤ 5, the melting point decreases with
increasing n. This can be explained by considering the
decreasing van der Waals forces between the long alkyl chains,
as shorter alkyl chains are brought into and disrupt the highly
ordered dodecyl chain stacks.
The trend changes around n = 6 can be related to structural
modifications and indicate the beginning of a new regular type
of molecular interaction. For n > 6, the melting points increases
with increasing n, due to the increasing van der Waals forces
between the long alkyl chains by addition of −CH2− group.
Furthermore, we observed an odd−even effect for 5 ≤ n ≤ 10
in the melting transitions. The fact that the melting points of
the compounds with even n are higher than their immediate
neighbors with odd lengths of n is surprising at first glance but
can be rationalized in terms of ion dynamics and in light of MD
simulations.26,27
dx.doi.org/10.1021/cg401396n | Cryst. Growth Des. 2014, 14, 1561−1571
Crystal Growth & Design
Figure 12. Schematic representation of the layer spacing distances d
[Å] of all the compounds in the crystalline and the ionic liquid
crystalline states. The layer spacing in crystalline states is plotted in
black and in liquid crystalline phases in red. Only the d values obtained
from the (001) reflections are shown. For compounds C2C12 and
C6C12, no mesophase was observed. For compound C3C12 and
C4C12, and C5C12, no layer spacing could be measured due to the
experimental limits and low crystallization temperatures. For
compounds exhibiting more than one crystalline polymorph at low
temperatures, only the d spacing at room temperature was given.
Figure 13. Illustration of the changes in the molecular arrangement of
C0C12 and C12C12 from the crystalline state to the mesophase.
The liquid crystalline properties of mesomorphic compounds
were examined by differential scanning calorimetry and
polarized optical microscopy. Combing the informations
obtained from POM images and X-ray scattering experiments
at small angle range, the mesophases that they form can be
identified as the smectic phase for these compounds.
Observations from SAXS measurements indicate that C0C12,
C1C12, C12C12, and C13C12 form smectic A phase, while
C7C12, C8C12, C9C12, C10C12, and C11C12 show smectic
C formations. Unequivocal mesophase identification for
compounds C3C12, C4C12, and C5C12 is not possible due
to the low temperature transitions lying beyond experimental
limits.
Finally, no thermic mesophase formation was observed for
C2C12 and C6C12. However, both of the compounds contain
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dodecyl units, which should according to our conclusions from
section 2 arouse a mesophase. This indicates the inadequacy of
a dodecyl group in guaranteeing mesophase formation. Crystal
structure analysis shows for C2C12 a bilayer lamellar structure
with a separation of hydrophobic (alkyl chains stacks) and
hydrophilic (imidazolium head groups) regions in the cations.
Remarkably, the arrangement of imidazolium cores in the
hydrophilic parts is very complicated, due to multiple
nonclassical hydrogen bonds between bromide anions and
imidazolium head groups, which hinder intensive interdigita-
tions of long chains. Therefore, we propose that a similar
system with less hydrogen bonds in the hydrophilic region
could improve liquid crystalline properties. Our further work
will focus on reducing the number of H-bond donors in the
hydrophilic core by replacing the 2-H proton on the
imidazolium cation by a methyl group. Additional experiments
on similar 2-methylimidazolium-based ILs bearing a dodecyl
group with different sizes and symmetries are required to gauge
the importance of such H-bond interactions.
■
ASSOCIATED CONTENT
*
S Supporting Information
Table S1: Thermal behavior of n-alkyl-dodecylimidazolium
bromide ionic liquids and ionic liquid crystals; SAXS
measurements; synthesis of 1-dodecylimidazole; crystallo-
graphic information file. This material is available free of
charge via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: anja.mudring@ruhr-uni-bochum.de. Tel: +49-234-32-
27408.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the German Science Foundation
DFG through the priority program 1191“Ionic Liquids”, the
DFG Cluster of Excellence RESOLV, and the DESY
(Deutsches Elektronensynchrotron Proposal No. I-
20100011). We thank Dr. Sergio Funari for support during
the SAXS measurements and thank Dr. P. Campbell for helpful
comments.
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